Polyarylethersulphone and polyamide-based thermoplastic mouldable masses with improved processing characteristics

ABSTRACT

Molding compositions comprise
         A) from 1 to 98.8% by weight of at least one polyarylene ether sulfone,   B) from 1 to 98.8% by weight of at least one thermoplastic polyamide,   C) from 0.1 to 60% by weight of at least one filler,   D) from 0 to 40% by weight of at least one impact-modifying rubber,   E) from 0 to 40% by weight of one or more different additives, and   F) from 0.1 to 30% by weight of at least one thermotropic polymer,
 
where the total of the percentages by weight of components A to F is 100%, wherein component B has a viscosity number of from 180 to 350 ml/g (measured in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid to DIN 53 727).

The present invention relates to molding compositions which comprise

-   -   A) from 1 to 98.8% by weight of at least one polyarylene ether        sulfone,    -   B) from 1 to 98.8% by weight of at least one thermoplastic        polyamide,    -   C) from 0.1 to 60% by weight of at least one filler,    -   D) from 0 to 40% by weight of at least one impact-modifying        rubber,    -   E) from 0 to 40% by weight of one or more different additives,        and    -   F) from 0.1 to 30% by weight of at least one thermotropic        polymer,        where the total of the percentages by weight of components A to        F is 100%, wherein component B has a viscosity number of from        180 to 350 ml/g (measured in a 0.5% strength by weight solution        in 96% strength by weight sulfuric acid to DIN 53 727).

The present invention further relates to the use of these moldingcompositions for producing moldings, films or fibers, and also to theresultant moldings, films or fibers.

Molding compositions based on polyarylene ether sulfones and onpolyamides are well known. Molding compositions of this type usuallyhave better flow properties than pure polyarylene ether sulfones.

Blends made from polyarylene ether sulfones with polyamides having atleast 50% by weight of hexamethylene terephthalamide units weredisclosed in EP-A 477 757. Other components mentioned in these blendsinclude entirely aromatic, thermoplastic, liquid-crystalline polyesters.In the blends mentioned preference is given to polyamides with viscositynumbers of up to 140 ml/g (corresponding to η_(red) of 1.4 dl/g), sincepolyamides with higher viscosity numbers also have high melt viscositiesand the blends prepared from these are difficult to process.

The German Patent Application with file reference number 19839331.8describes blends made from polyarylene ether sulfones with polyamideshaving viscosity numbers of at least 180 ml/g, which in additioncomprise stabilizers based on copper bromide or copper iodide. Whenthese blends are exposed to high temperatures for long periods theirmechanical properties are only slightly impaired.

It is an object of the present invention to provide thermoplasticmolding compositions which are based on polyarylene ether sulfones andon polyamides and which have good mechanical properties together withimproved flowability and stability during processing, in particular meltstability.

We have found that this object is achieved by the molding compositionsdefined at the outset and described in more detail below.

Component A

The novel molding compositions comprise, based on the total weight of Ato F, from 1 to 98.8% by weight, in particular from 7.5 to 92.19% byweight and particularly preferably from 10 to 88.49% by weight, ofcomponent A.

According to the invention a polyarylene ether sulfone is used ascomponent A. The component A used may also be a mixture made from two ormore different polyarylene ether sulfones.

The arylene groups of the polyarylene ether sulfones A may be identicalor different and, independently of one another, are an aromatic radicalhaving from 6 to 18 carbon atoms. Examples of suitable arylene radicalsare phenylene, biphenylene, terphenylene, 1,5-naphthylene,1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene and 2,6-anthrylene.Among these, preference is given to 1,4-phenylene and 4,4′-biphenylene.These aromatic radicals are preferably unsubstituted. However, they mayhave one or more substituents. Examples of suitable substituents arealkyl, arylalkyl, aryl, nitro, cyano and alkoxy groups, and alsoheteroaromatics, such as pyridine, and halogen. Preferred substituentsinclude alkyl having up to 10 carbon atoms, such as methyl, ethyl,isopropyl, n-hexyl and isohexyl, C₁-C₁₀-alkoxy, such as methoxy, ethoxy,n-propoxy and n-butoxy, aryl having up to 20 carbon atoms, such asphenyl or naphthyl, and also fluorine and chlorine.

Other preferred substituents are those obtainable by reacting thepolyarylene ether sulfones with a reactive compound which has, besides acarbon-carbon double or triple bond, one or more carbonyl, carboxylicacid, carboxylate, anhydride, amide, imide, carboxylic ester, amino,hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups.The bonding of the arylene groups to one another in the polyaryleneether sulfones may be via —SO₂—, or, for example, via —O—, —S—, —SO—,—CO—, —N═N—, —COO—, or via an unsubstituted or substituted alkyleneradical, or via a chemical bond.

Preferred polyarylene ether sulfones which can be used according to theinvention (component A) have a structure made from repeat units of theformula I

where

-   -   t and q, independently of one another, are 0, 1, 2 or 3,    -   each of Q, T and Z, independently of one another, is a chemical        bond or a group selected from the class consisting of —O—, —S—,        —SO₂—, S═O, C═O, —N═N—, —R^(a)C═CR^(b)— and —CR^(c)R^(d)—,        -   each of R^(a) and R^(b), independently of one another, is            hydrogen or C₁-C₁₂-alkyl and        -   each of R^(c) and R^(d), independently of one another, is            hydrogen or C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy or C₆-C₁₈-aryl,            where, if desired, R^(c) and R^(d), if they are alkyl,            alkoxy or aryl, may independently of one another have            fluorine and/or chlorine substituents or, together with the            carbon atom to which they are bonded, may form a            C₃-C₁₂-cycloalkyl group, which may be unsubstituted or            substituted by one or more C₁-C₆-alkyl groups, with the            proviso that at least one of the groups T, Q and Z is —SO₂—            and, if t and q are O, Z is —SO₂—, and    -   Each of Ar and Ar¹, independently of one another, is        C₆-C₁₈-arylene, unsubstituted or substituted by C₁-C₁₂-alkyl,        C₆-C₁₈-aryl, C₁-C₁₂-alkoxy or halogen.

It is also possible for different units of the formula I to be presentin the polyarylene ether sulfone, distributed randomly or in blocks.

Polyarylene ethers A which can be used according to the invention may beprepared, for example, in a manner similar to that of GB 1 152 035 andU.S. Pat. No. 4,870,153, which are expressly incorporated herein by wayof reference. Examples of suitable process conditions for the synthesisof polyarylene ether sulfones are described in EP-A-0 113 112 and EP-A-0135 130. The reaction of the monomers in aprotic polar solvents in thepresence of anhydrous alkali metal carbonate is particularly suitable. Aparticularly preferred combination is N-methylpyrrolidone as solvent andpotassium carbonate as catalyst. The reaction in the melt is similarlypreferred. Examples of suitable polyarylene ether sulfones A are thosehaving at least one of the following repeat structural units I₁ to I₁₅:

Particularly preferred units of the formula I are those of the formulaeI₁, and I₂, individually or mixed.

Depending on the conditions for the synthesis, the polyarylene ethersulfones may have various groups. These groups may have bonding to atomsof the polymer chain or be end groups of the polymer chain. These groupsinclude those which are inert to component B and those which can reactwith polyamides B, in particular with the amino and carboxyl groups.

Inert groups include halo, in particular chloro, alkoxy, particularlymethoxy or ethoxy, aryloxy, preferably phenoxy, and benzyloxy groups.Examples of reactive groups are hydroxyl, amino, anhydride, epoxy andcarboxyl. Particular preference is given to polyarylene ether sulfoneshaving amino, anhydride or epoxy end groups or a mixture of these.

In one embodiment, the novel molding compositions comprise polyaryleneether sulfones A which are essentially free from reactive groups.However, in a preferred embodiment, a mixture of different polyaryleneether sulfones having inert and reactive groups may be used. Theproportion of polyarylene ether sulfones having reactive groups may befrom 2 to 98% by weight, preferably from 5 to 50% by weight, based oncomponent A.

A particularly suitable component A is a mixture made from at least onepolyarylene ether sulfone al having groups which are inert to thepolyamides B and from at least one polyarylene ether sulfone a2 whichcontains groups which can react with the polyamides B.

Particularly suitable groups which may be mentioned in the polyaryleneether sulfones a2 are anhydride, carboxyl, epoxy or amino groups or amixture of these.

In one embodiment, the preferred polyarylene ether sulfones include, inparticular in a mixture with polyarylene ether sulfones which containinert groups, carboxyl-containing polyarylene ether sulfones havingrepeat structural units of formulae I and II

where the variables and radicals are as defined above and

-   -   R¹ is H, C₁-C₆-alkyl or —(CH₂)_(n)—COOH,    -   n is an integer from 0 to 6,    -   each of Ar² and Ar^(3,) independently of one another, is        C₆-C₁₈-arylene, and these may have substitution by one or more        C₁-C₁₂-alkyl, C₆-C₁₈-aryl or C₁-C₁₂-alkoxy groups, or by        halogen, and    -   Y is a chemical bond or a group selected from the class        consisting of —O—, —S—, —SO₂—, S═O, C═O, —N═N—, —R^(a)C═CR^(b)—        and —CR^(c)R^(d)—.

These carboxyl-containing polyarylene ethers are obtainable, forexample, by methods similar to the processes described in EP-A-0 185237, or else those described by I. W. Parsons et al., in Polymer, 34,2836 (1993) and T. Koch, H. Ritter, in Macromol. Phys. 195, 1709 (1994).

Examples of suitable structural elements II are:

where each n is 0, 1, 2, 3, 4, 5 or 6.

The polyarylene ether sulfones containing acid groups have viscositynumbers of from about 15 to 80 ml/g (determined in 1% strength NMPsolution at 25° C.). If these polyarylene ether sulfones containing acidgroups are used, the proportion of free acid groups in component A ispreferably from 0.05 to 25 mol %, preferably from 0.1 to 20 mol % and inparticular from 0.1 to 15 mol %. The proportion of acid groups isdetermined by ¹H-NMR, as described by I. W. Parsons et al., Polymer, 34,2836 (1993).

Polyarylene ether sulfones A having hydroxyl end groups may be prepared,for example, by suitably selecting the molar ratio between dihydroxymonomers and dichloro monomers (see, for example, McGrath et al Polym.Eng. Sci. 17, 647 (1977); Elias “Makromoleküle” 4th Edn. (1981) pp.490-493, Hüitig & Wepf. Verlag, Basle).

Polyarylene ether sulfones A which have amino end groups may, forexample, be obtained via the presence of p-aminophenol during thepolymerization (J. E. Mc. Grath, Polymer 30, 1552 (1989)).

The preparation of polyarylene ether sulfones containing anhydride endgroups is described, for example, in DE-A 44 29 107. Other suitablepolyarylene ether sulfones, grafted with anhydrides, may be prepared asdescribed in EP-A 513 488.

Polyarylene ether sulfones having epoxy end groups can be prepared frompolyarylene ether sulfones having OH end groups by, for example,reacting the latter with suitable compounds which have propylene oxidegroups or from which propylene oxide groups are obtainable, preferablyepichlorohydrin.

The reaction of the hydroxyl-terminated polyarylene ether sulfones withepichlorohydrin preferably takes place at from 30 to 200° C. in asolvent. Examples of suitable solvents for this are aliphatic oraromatic sulfoxides or sulfones, or else N-methylpyrrolidone. Thereaction is generally carried out in a weakly basic medium to avoid, asfar as possible, ring-opening of the epoxy groups.

The polyarylene ether sulfones A may also be (block) copolymers whichcontain polyarylene ether sulfone segments and segments of otherthermoplastic polymers, such as polyesters, aromatic polycarbonates,polyester carbonates, polysiloxanes, polyimides or polyetherimides. Themolar masses (number-average) of the blocks or of the graft branches inthe copolymers are generally from 1000 to 30,000 g/mol. The blocks ofdifferent structure may have an alternating or random arrangement. Theproportion by weight of the polyarylene ether sulfones in the (block)copolymers is generally at least 10% by weight. The proportion by weightof the polyarylene ether sulfones may be up to 97% by weight. Preferenceis given to (block) copolymers with a proportion by weight of up to 90%by weight of polyarylene ether sulfones. Particularly preferred (block)copolymers have from 20 to 80% by weight of polyarylene ether sulfones.

The average molar masses Mn (number-average) of the polyarylene ethersulfones are generally from 5000 to 60,000 g/mol, and their relativeviscosities are generally from 0.20 to 0.95 dl/g. Depending on thesolubility of the polyarylene ether sulfones, the relative viscositiesare determined either in 1% strength by weight N-methylpyrrolidonesolution, in mixtures made from phenol and dichlorobenzene, or in 96%strength sulfuric acid, in each case at 20 or 25° C.

Component B

Based on the total weight of A to F, from 1 to 98.8% by weight, inparticular from 7.5 to 92.19% by weight, particularly preferably from 10to 88.49% by weight of component B is present in the novel moldingcompositions.

The component B used according to the invention is one or morethermoplastic polyamides which have a viscosity number of from 180 to350 ml/g, particularly preferably from 190 to 350 ml/g, in particularfrom 190 to 240 ml/g (measured in 0.5% strength by weight solution in96% strength by weight sulfuric acid to DIN 53 727).

Suitable polyamides may be semicrystalline or amorphous resins with amolecular weight M_(w) (weight-average) of at least 5000, for example asdescribed in the U.S. Pat. Nos. 2,071,250, 2,071,251, 2,130,523,2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210.

Examples of these are polyamides which derive from lactams having from 7to 13 ring members, such as polycaprolactam, polycaprylolactam orpolylaurolactam, and also polyamides which are obtained by reactingdicarboxylic acids with diamines.

Polyamides B may, for example, be prepared by condensing equimolaramounts of a saturated or aromatic dicarboxylic acid having from 4 to 16carbon atoms with a saturated or aromatic diamine which has up to 16carbon atoms, or by condensing ω-aminocarboxylic acids or, respectively,polyaddition of corresponding lactams.

Other polyamides suitable according to the invention are aliphatic(co)polyamides.

Particular examples of dicarboxylic acids in aliphatic polyamides arealkanedicarboxylic acids having from 6 to 12 carbon atoms, in particularfrom 6 to 10 carbon atoms. Merely by way of example, mention may be madehere of adipic acid, suberic acid, azelaic acid, sebacic acid anddodecanedioic acid.

Preferred suitable diamines in aliphatic polyamides are alkanediamineshaving from 4 to 12 carbon atoms, in particular from 4 to 8 carbonatoms, for example 1,4-butanediamine, 1,5-pentanediamine and piperazineand the cyclic diamines

-   di(4-aminocyclohexyl)methane and-   2,2-di(4-aminocyclohexyl)propane.

It is, of course, also possible to use aminocarboxylic acids or,respectively, the corresponding lactams having, for example, from 6 to13 carbon atoms as polyamide-forming monomers for aliphatic polyamides.Examples of suitable monomers of this type are caprolactam,caprylolactam, enantholactam, ω-aminoundecanoic acid and laurolactam.

Examples of preferred aliphatic polyamides are

-   polyhexamethyleneadipamide (nylon-6,6),-   polyhexamethyleneazelamide (nylon-6,9),-   polyhexamethylenesebacamide (nylon-6,10), and-   polyhexamethylenedodecandiamide (nylon-6,12), the polyamides    obtained via ring-opening of lactams, such as polycaprolactam and    polylaurolactam, and also poly-11-aminoundecanoic acid and a    polyamide made from di(p-aminocyclohexyl)methane and-   dodecanedioic acid, and also the copolyamides nylon-6/6-6, in    particular with a proportion of from 5 to 95% by weight of    caprolactam units.

Other polyamides which should be mentioned are those obtainable, forexample, by condensing 1,4-diaminobutane with adipic acid at an elevatedtemperature (nylon-4,6). Preparation processes for polyamides of thisstructure are described, for example, in EP-A 38 094, EP-A 38 582 andEP-A 39 524.

Other suitable polyamides are those obtainable by copolymerizing two ormore of the abovementioned monomers, and mixtures of two or morepolyamides, in any desired mixing ratio.

A preferred embodiment of the invention uses partly aromatic polyamides.These may be prepared by copolycondensing, for example, adipic acid,isophthalic acid and/or terephthalic acid with hexamethylenediamine orcopolycondensing caprolactam and terephthalic acid withhexamethylenediamine. Partly aromatic copolyamides of this typepreferably contain, as component b₁, from 20 to 90% by weight of unitswhich derive from terephthalic acid and from hexamethylenediamine. Asmall proportion of the terephthalic acid, preferably not more than 10%by weight of all of the aromatic dicarboxylic acids used, may bereplaced by isophthalic acid or by other aromatic dicarboxylic acids,preferably those where the carboxyl groups are in para position.

Besides the units which derive from terephthalic acid and fromhexamethylenediamine, the partly aromatic copolyamides may contain units(b₂) which derive from ε-caprolactam and/or units (b₃) which derive fromadipic acid and from hexamethylenediamine.

The proportion of units b₂ which derive from ε-caprolactam is usuallyfrom 10 to 80% by weight, preferably from 20 to 50% by weight, inparticular from 25 to 40% by weight, while the proportion of units b₃which derive from adipic acid and from hexamethylenediamine is up to 70%by weight, preferably from 30 to 60% by weight and in particular from 35to 55% by weight. The total of the percentages by weight of componentsb₁ to b₃ is always 100.

In the case of copolyamides which contain units of ε-caprolactam andalso units of adipic acid and hexamethylenediamine, care should be takenthat the proportion of units which are free from aromatic groups is atleast 10% by weight, preferably at least 20% by weight. The ratio ofunits which derive from ε-caprolactam and from adipic acid and fromhexamethylenediamine is not subject here to any particular limitation.

In another embodiment, component B is composed of, based on the totalweight of component B, from 40 to 100% by weight, preferably from 50 to100% by weight and in particular from 70 to 100% by weight, of a partlyaromatic, semicrystalline, thermoplastic polyamide which has been builtup from

-   -   b′₁) from 30 to 44 mol %, preferably from 32 to 40 mol % and in        particular from 32 to 38 mol %, of units which derive from        terephthalic acid,    -   b′₂) from 6 to 20 mol %, preferably from 10 to 18 mol % and in        particular from 12 to 18 mol %, of units which derive from        isophthalic acid,    -   b′₃) from 43 to 49.5 mol %, preferably from 46 to 48.5 mol % and        in particular from 46.3 to 48.2 mol %, of units which derive        from hexamethylenediamine, and    -   b′₄) from 0.5 to 7 mol %, preferably from 1.5 to 4 mol % and in        particular from 1.8 to 3.7 mol %, of units which derive from        cyclic aliphatic diamines having from 6 to 30 carbon atoms,        preferably from 13 to 29 carbon atoms and in particular from to        17 carbon atoms,

-   where the total of the molar percentages of components b′₁ to b′₄ is    100%.

The diamine units b′₃ and b′₄ are preferably reacted in equimolarquantities with the dicarboxylic acid units b′₁ and b′₂.

Preferred suitable monomers b′₄ are cyclic diamines of the formula (III)

where

-   R² is hydrogen or C₁-C₄-alkyl,    -   R³ is C₁-C₄-alkyl or hydrogen, and    -   R⁴ is C₁-C₄-alkyl or hydrogen.

Preferred diamines b′₄ are bis(4-aminocyclohexyl)methane,

-   bis(4-amino-3-methylcyclohexyl)methane,-   bis(4-aminocyclohexyl)-2,2′-propane and-   bis(4-amino-3-methylcyclohexyl)-2,2′-propane.

Other monomers b′₄ which may be mentioned are 1,3- and1,4-cyclohexanediamine and isophoronediamine.

Besides the units b′₁ to b′₄ described above, the partly aromaticcopolyamides B may contain, based on B, up to 4% by weight, preferablyup to 3.5% by weight, of other polyamide-forming monomers b′₅, as knownfrom other polyamides.

Possible other polyamide-forming monomers b′₅ are aromatic dicarboxylicacids which have from 8 to 16 carbon atoms. Examples of suitablearomatic dicarboxylic acids are substituted terephthalic and isophthalicacids, such as 3-tert-butylisophthalic acid, polycyclic dicarboxylicacids, e.g. 4,4′- and 3,3′-diphenyldicarboxylic acid, 4,4′- and3,3′-diphenylmethanedicarboxylic acid, 4,4′- and 3,3′-diphenyl sulfonedicarboxylic acid, 1,4- and 2,6-naphthalenedicarboxylic acid andphenoxyterephthalic acid.

Other polyamide-forming monomers b′₅ may derive from dicarboxylic acidshaving from 4 to 16 carbon atoms and from aliphatic diamines having from4 to 16 carbon atoms, or else from aminocarboxylic acids or,respectively, from corresponding lactams having from 7 to 12 carbonatoms. Suitable monomers of these types which may be mentioned heremerely as examples are suberic acid, azelaic acid and sebacic acid asrepresentatives of the aliphatic dicarboxylic acids, and1,4-butanediamine, 1,5-pentanediamine and piperazine as representativesof the diamines, and caprolactam, caprylolactam, enantholactam,ω-aminoundecanoic acid and laurolactam as representatives of lactams or,respectively, aminocarboxylic acids.

Preferred partly aromatic copolyamides B have triamine contents below0.5% by weight, preferably below 0.3% by weight.

Compared with products of the same composition but higher triaminecontent, copolyamides with a low triamine content have lower meltviscosities at the same solution viscosity. This considerably improvesboth processability and product properties.

The melting points of the partly aromatic copolyamides are from 270 to340° C., preferably from 280 to 330° C., and this melting point isassociated with a high glass transition temperature, generally 110° C.or above, in particular above 130° C. (in the dry state).

Partly aromatic copolyamides B generally feature degrees ofcrystallinity of >30%, preferably >35%, and in particular >40%.

The degree of crystallinity is a measure of the proportion ofcrystalline fragments in the copolyamide and is determined by X-rayscattering or indirectly by measuring ΔH_(crist.).

It is, of course, also possible to use mixtures of different partlyaromatic copolyamides, or else mixtures made from aliphatic and frompartly aromatic (co)polyamides, and in each case the mixing ratio may beas desired.

Suitable processes for preparing the polyamides B are known to theskilled worker.

A preferred method of preparation is the batch process. For this, theaqueous monomer solution is heated in an autoclave within a period offrom 0.5 to 3 h to 280-340° C., achieving a pressure of from 10 to 50bar, in particular from 15 to 40 bar, and this pressure is held assteady as possible for up to 2 h by releasing excess water vapor. Thepressure in the autoclave is then reduced at constant temperature withina period of from 0.5 to 2 h to give a final pressure of from 1 to 5 bar.The polymer melt is then discharged, cooled and pelletized.

Another process is based on those described in EP-A 129195 and 129 196.To prepare partly aromatic copolyamides, for example, by this method anaqueous solution of the monomers b′₁) to b′₄), and also, if desired,b′₅), with a monomer content of from 30 to 70% by weight, preferablyfrom 40 to 65% by weight, is heated to 280-330° C. at elevated pressure(from 1 to 10 bar) for a period of less than 60 s with simultaneousevaporation of water and formation of a prepolymer. The prepolymer andvapor are then continuously separated and the vapor rectified, and theentrained diamines passed back to the mixture. Finally, the prepolymeris passed to a polycondensation zone and polycondensed at a gaugepressure of from 1 to 10 bar at from 280 to 330° C. for a residence timeof from 5 to 30 min. The temperature in the reactor is, of course, abovethat required at the respective water-vapor pressure to melt theprepolymer being produced.

These short residence times substantially prevent the formation oftriamines.

The polyamide prepolymer obtained in the manner described and generallyhaving a viscosity number of from 40 to 70 ml/g, preferably from 40 to60 ml/g, measured on a 0.5% strength by weight solution in 96% strengthsulfuric acid at 25° C., is continuously removed from the condensationzone.

It is advantageous to pass the molten polyamide prepolymer through adischarge zone, at the same time removing the residual water present inthe melt. An example of a suitable discharge zone is a vented extruder.The melt freed from water may then be cast into extrudates andpelletized.

These pellets are condensed to the required viscosity in the solid phaseunder an inert gas, continuously or batchwise, at below the meltingpoint, e.g. from 170 to 240° C. For the batchwise solid-phasecondensation use may be made of tumbling dryers, for example, and forthe continuous solid-phase condensation use may be made of annealingtubes through which hot inert gas passes. Preference is given to thecontinuous solid-phase condensation, and the inert gas used is nitrogenor in particular superheated steam, advantageously the steam availableat the top of the column.

In another embodiment it is also possible for components A, C, F and, ifdesired, D and/or E to be added straightaway to the prepolymer ofcomponent B in the vented extruder, and in this case the vented extruderusually has suitable mixing elements, such as kneading blocks. This maylikewise be followed by discharge as an extrudate, cooling andpelletizing.

Component C

The novel molding compositions comprise from 0.1 to 60% by weight ofreinforcing agents or fillers. They preferably comprise from 0.1 to 50%by weight, in particular from 1 to 40% by weight, of fibrous orparticulate fillers or reinforcing materials, or mixtures of these. Eachof the amounts given is based on the total weight of components A to F.

Preferred fibrous fillers or fibrous reinforcing materials are carbonfibers, potassium titanate whiskers, aramid fibers and particularlypreferably glass fibers. If glass fibers are used they may have beenprovided with a size, preferably a polyurethane size, and with acoupling agent, to improve compatibility with the matrix material. Thecarbon fibers and glass fibers used generally have a diameter of from 6to 20 μm.

The glass fibers may be incorporated either as short glass fibers orelse as continuous-filament strands (rovings). The average length of theglass fibers in the finished injection molding is preferably from 0.08to 0.5 mm.

Carbon fibers or glass fibers may also be used as wovens, mats or glasssilk rovings.

Suitable particulate fillers are amorphous silica, carbonates, such asmagnesium carbonate or chalk, powdered quartz, mica, a very wide varietyof silicates, such as clays, muscovite, biotite, suzoite, tin maletite,talc, chlorite, phlogophite, feldspar, calcium silicates, such aswollastonite, or aluminum silicates, such as kaolin, particularlycalcined kaolin.

In a particularly preferred embodiment use is made of particulatefillers in which at least 95% by weight, preferably at least 98% byweight, of the particles have a diameter (maximum dimension) determinedon the finished product of less than 45 μm, preferably less than 40 μm,and of which the aspect ratio, determined on the finished product, isfrom 1 to 25, preferably from 2 to 20.

The particle diameters here may, for example, be determined by takingelectron micrographs of thin sections of the polymer mixture and usingat least 25, preferably at least 50, filler particles for theevaluation. The particle diameters may also be determined bysedimentation analysis as in Transactions of ASAE, page 491 (1983). Theproportion by weight of fillers of size below 40 μm may also be measuredby screen analysis. The aspect ratio is the ratio of particle diameterto thickness (largest to smallest dimension).

Particularly preferred particulate fillers are talc, kaolin, such ascalcined kaolin, and wollastonite and mixtures of two or all of thesefillers. Among these, particular preference is given to talc with aproportion of at least 95% by weight of particles of diameter less than40 μm and with an aspect ratio of from 1.5 to 25, determined in eachcase on the finished product. Kaolin preferably has a proportion of atleast 95% by weight of particles of diameter less than 20 μm and anaspect ratio of from 1.2 to 20, determined in each case on the finishedproduct.

Component D

The novel molding compositions may, if desired, compriseimpact-modifying rubbers D. The proportion of these is from 0 to 40% byweight, in particular from 0 to 25% by weight, particularly preferablyfrom 0 to 20% by weight, based on the total weight of A to F.

Component D may also be a mixture of two or more differentimpact-modifying rubbers.

For the purposes of the present invention, rubbers are generallycrosslinkable polymers which have elastomeric properties at roomtemperature.

Preferred rubbers which increase the toughness of molding compositionsusually have two significant features: they comprise an elastomericfraction which has a glass transition temperature below −10° C.,preferably below −30° C., and they contain at least one functional groupwhich can interact with the polyamide B or polyarylene sulfone A.Examples of suitable functional groups are carboxylic acid, carboxylicanhydride, carboxylic ester, carboxamide, carboximide, amino, hydroxyl,epoxy, urethane and oxazoline groups.

Preferred functionalized rubbers D include functionalized polyolefinrubbers built up from the following components:

-   -   d₁) from 40 to 99% by weight of at least one α-olefin having        from 2 to 8 carbon atoms;    -   d₂) from 0 to 50% by weight of a diene;    -   d₃) from 0 to 45% by weight of a C₁-C₁₂-alkyl ester of acrylic        or methacrylic acid, or mixtures of esters of this type;    -   d₄) from 0 to 40% by weight of an ethylenically unsaturated        C₂-C₂₀ mono- or dicarboxylic acid or of a functional derivative        of an acid of this type;    -   d₅) from 1 to 40% by weight of a monomer containing epoxy        groups; and    -   d₆) from 0 to 5% by weight of other monomers capable of        free-radical polymerization.

Examples of suitable α-olefins d₁ are ethylene, propylene, 1-butylene,1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene,3-methyl-1-butylene and 3-ethyl-1-butylene. Ethylene and propylene arepreferred.

Examples of suitable diene monomers d₂ are conjugated dienes having from4 to 8 carbon atoms, such as isoprene and butadiene, nonconjugateddienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene,1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes,cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes, suchas 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene,2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, andtricyclodienes, such as 3-methyltricyclo[5.2.1.0^(2,6)]-3,8-decadiene,or mixtures of these. Preference is given to 1,5-hexadiene,5-ethylidenenorbornene and dicyclopentadiene. The diene content isgenerally from 0 to 50% by weight, preferably from 0.5 to 50% by weight,in particular from 2 to 20% by weight and particularly preferably from 3to 15% by weight, based on the total weight of the olefin polymer.

Examples of suitable esters d₃ are methyl, ethyl, propyl, n-butyl,isobutyl, 2-ethylhexyl, octyl and decyl acrylates and the correspondingmethacrylates. Among these particular preference is given to methyl,ethyl, propyl, n-butyl and 2-ethylhexyl acrylate and methacrylate.

Instead of the esters d₃, or in addition to these, the olefin polymersmay also comprise acid-functional and/or latently acid-functionalmonomers in the form of ethylenically unsaturated mono- or dicarboxylicacids d₄.

Examples of monomers d₄ are acrylic acid, methacrylic acid, tertiaryalkyl esters of these acids, in particular tert-butyl acrylate, anddicarboxylic acids, such as maleic acid and fumaric acid, andderivatives of these acids, and also their half-esters.

For the purposes of the invention, latently acid-functional monomers arethose compounds which under the conditions of the polymerization orduring incorporation of the olefin polymers into the moldingcompositions form free acid groups. Examples of these are anhydrides ofdicarboxylic acids having from 2 to 20 carbon atoms, in particularmaleic anhydride, and tertiary C₁-C₁₂-alkyl esters of the abovementionedacids, in particular tert-butyl acrylate and tert-butyl methacrylate.Ethylenically unsaturated dicarboxylic acids and anhydrides d₄ have thefollowing formulae IV and V:

R⁵(COOR⁶)C═C(COOR⁷)R⁸  (IV)

where R⁵, R⁶, R⁷ and R⁸, independently of one another, are H orC₁-C₆-alkyl.

Monomers d₅ containing epoxy groups have the following formulae VI andVII

where R⁹, R¹⁰, R¹¹ and R¹², independently of one another, are H orC₁-C₆-alkyl, m is an integer from 0 to 20, and p is an integer from 0 to10.

R⁵ to R¹² are preferably hydrogen, m is preferably 0 or 1 and p ispreferably 1.

Preferred compounds d₄ and, respectively, d₅ are maleic acid, fumaricacid and maleic anhydride and, respectively, alkenyl glycidyl ethers andvinyl glycidyl ether.

Particularly preferred compounds of the formulae IV and V and,respectively, VI and VII are maleic acid and maleic anhydride and,respectively, acrylates and/or methacrylates both of which contain epoxygroups, in particular glycidyl acrylate and glycidyl methacrylate.

Particularly preferred olefin polymers are those made from

-   -   from 49.9 to 98.9% by weight, in particular from 59.85 to 94.85%        by weight, of ethylene, and    -   from 1 to 50% by weight, in particular from 5 to 40% by weight,        of an ester of acrylic or methacrylic acid, and    -   from 0.1 to 20.0% by weight, in particular from 0.15 to 15% by        weight, of glycidyl acrylate and/or glycidyl methacrylate,        acrylic acid and/or maleic anhydride.

Particularly suitable functionalized rubbers D are

-   ethylene-methyl methacrylate-glycidyl methacrylate polymers,-   ethylene-methyl acrylate-glycidyl methacrylate polymers,-   ethylene-methyl acrylate-glycidyl acrylate polymers and-   ethylene-methyl methacrylate-glycidyl acrylate polymers.

Examples of other monomers d₆ are vinyl esters and vinyl ethers andmixtures of these.

The polymers described above may be prepared by processes known per se,preferably by random copolymerization at high pressure and elevatedtemperature.

The melt index of the copolymers is generally from 1 to 80 g/min 10 min(measured at 190° C. and 2.16 kg load).

Core-shell graft rubbers are another group of suitable rubbers. Theseare graft rubbers prepared in emulsion and composed of at least one hardand one soft constituent. Usually, a hard constituent is a polymer witha glass transition temperature of at least 25° C., and a softconstituent is a polymer with a glass transition temperature of not morethan 0° C. These products have a structure made from a core (graft base)and from at least one shell (graft), and the structure is a result ofthe sequence of addition of the monomers. The soft constituentsgenerally derive from butadiene, isoprene, alkyl acrylates, alkylmethacrylates or siloxanes and, if desired, other comonomers. Suitablesiloxane cores may be prepared, for example, starting from cyclicoligomeric octamethyltetrasiloxane or fromtetravinyltetramethyltetrasiloxane. These may, for example, be reactedwith γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationicpolymerization, preferably in the presence of sulfonic acids, to givethe soft siloxane cores. The siloxanes may also be crosslinked by, forexample, carrying out the polymerization in the presence of silaneshaving hydrolyzable groups, such as halo or alkoxy, for exampletetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane.Examples of suitable comonomers for this are styrene, acrylonitrile andcrosslinking or grafting monomers having more than one polymerizabledouble bond, for example diallyl phthalate, divinylbenzene, butanedioldiacrylate or triallyl (iso)cyanurate. The hard constituents generallyderive from styrene, α-methylstyrene or from copolymers of these, andpreferred comonomers here are acrylonitrile, methacrylonitrile andmethyl methacrylate.

Preferred core-shell graft rubbers comprise a soft core and a hard shellor a hard core, a first soft shell and at least one further hard shell.The incorporation of functional groups here, such as carbonyl,carboxylic acid, anhydride, amide, imide, carboxylic ester, amino,hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups,preferably takes place by adding suitably functionalized monomers duringthe polymerization of the final shell. Examples of suitablefunctionalized monomers are maleic acid, maleic anhydride, half-estersor diesters, or maleic acid, tert-butyl (meth)acrylate, acrylic acid,glycidyl (meth)acrylate and vinyloxazoline. The proportion of monomerswith functional groups is generally from 0.1 to 25% by weight,preferably from 0.25 to 15% by weight, based on the total weight of thecore-shell graft rubber. The weight ratio of soft to hard constituentsis generally from 1:9 to 9:1, preferably from 3:7 to 8:2.

Rubbers of this type are known per se and are described, for example, inEP-A 208 187.

Thermoplastic polyester elastomers are another group of suitable impactmodifiers. For the purposes of the invention, polyester elastomers aresegmented copolyetheresters which comprise long-chain segments generallyderiving from poly(alkylene) ether glycols and short-chain segmentsderiving from low-molecular-weight diols and dicarboxylic acids.Products of this type are known per se and are described in theliterature, for example in U.S. Pat. No. 3,651,014. Correspondingproducts are also available commercially as Hytrel® (Du Pont), Arnitel®(Akzo) and Pelprene® (Toyobo Co. Ltd.).

It is also, of course, possible to use mixtures of various rubbers.

Component E

The novel molding compositions may comprise, as component E, additives,such as processing aids, pigments, stabilizers, flame retardants, ormixtures of various additives. Other examples of customary additives areoxidation retarders, agents to inhibit decomposition caused by heat orby ultraviolet light, lucricants, mold-release agents, dyes andplasticizers.

Their proportion, based on the total weight of components A to F, isaccording to the invention from 0 to 40% by weight, preferably from 0.01to 20% by weight, in particular from 0.01 to 15% by weight. (Trans22/30-34)

Pigments and dyes are generally present in amounts of up to 6% byweight, preferably from 0.5 to 5% by weight and in particular from 0.5to 3% by weight where component E comprises stabilizers, the proportionthereof is usually up to 2% by weight, preferably from 0.01 to 1% byweight, in particular from 0.01 to 0.5% by weight, based on the totalweight of A to F.

The pigments for coloration of thermoplastics are well known: see forexample R. Gächter and H. Müller, Taschenbuch der Kunststoffadditive,Carl Hanser Verlag, 1983, pp. 494-510. A first preferred group ofpigments is that of white pigments, such as zinc oxide, zinc sulfide,white lead (2 PbCO₃.Pb(OH)₂), lithopones, antimony white and titaniumdioxide. Of the two most common crystal forms of titanium dioxide(rutile and anatase) it is the rutile form in particular which is usedfor white coloration of the novel molding compositions.

Black pigments which may be used according to the invention are ironoxide black (Fe₃O₄), spinel black (Cu(Cr,Fe)₂O₄), manganese black (amixture of manganese dioxide, silica and iron oxide), cobalt black andantimony black, and particularly preferably carbon black, usually usedin the form of furnace black or gas black (see in this connection G.Benzing, Pigmente für Anstrichmittel, Expert-Verlag (1988), pp. 78ff.).

Inorganic color pigments, such as chromium oxide green, or organic colorpigments, such as azo pigments and phthalocyanines, may, of course, beused according to the invention to achieve particular shades of color.Pigments of this type are widely available commercially.

Examples of oxidation inhibitors and heat stabilizers which according tothe invention may be added to the thermoplastic compositions are halidesof metals of Group I of the Periodic Table, e.g. those of sodium, ofpotassium or of lithium for example chlorides, bromides or iodides. Itis also possible to use zinc fluoride and zinc chloride. Other compoundswhich may be used are sterically hindered phenols, hydroquinones,substituted representatives of this class, secondary aromatic amines, ifdesired combined with phosphorus-containing acids and/or salts of these,and mixtures of these compounds, preferably in concentrations of up to1% by weight, based on the weight of the mixture A to F.

A particularly preferred component E added to the novel moldingcompositions is copper(I) chloride, copper(I) bromide or copper(I)iodide or a mixture of these. Copper(I) iodide is preferably used. Theamount used here is generally from 0.01 to 1.0% by weight, preferablyfrom 0.01 to 0.5% by weight, based on the total weight of A to F.

Examples of UV stabilizers are various substituted resorcinols,salicylates, benzotriazoles and benzophenones, and the amounts of theseused are usually up to 2% by weight.

Lubricants and mold-release agents, generally added in amounts of up to1% by weight to the thermoplastic composition, are stearic acid, stearylalcohol, alkyl stearates and stearamides, and also esters ofpentaerythritol with long-chain fatty acids. It is also possible to usestearates of calcium, of zinc or of aluminum, and also dialkyl ketones,e.g. distearyl ketone.

Other possible additives are nucleating agents, such as talc.

Component F

The proportion of component F in the novel molding compositions is from0.1 to 30% by weight, based on the total weight of components A to F.The amount of component F in the novel molding compositions, based ineach case on the total weight of components A to F, is preferably from0.2 to 20% by weight, in particular from 0.5 to 10% by weight.

The materials of component F are thermotropic polymers. For the purposesof the present invention, thermotropic polymers are polymers which haveliquid-crystalline properties over a particular temperature range.Particularly suitable components F comprise thermotropic polymers whichare liquid-crystalline over a temperature range within which the novelmolding compositions are processed. The temperature T_(k) of thetransition of the liquid-crystalline phase into the melt for thepolymers suitable as component F is generally 350° C. or below. Thetemperature T_(k) of the transition is 300° C. or below for preferredliquid-crystalline polymers F. The temperature T_(k) of the transitionis in particular from 200 to 350° C.

Possible components F are generally thermotropic polyesters,thermotropic polyesteramides or thermotropic polyamides.

It is preferable for entirely aromatic polyesters or copolyesters to beused as component F. By way of example, suitable liquid-crystallinepolymers have the repeat structural units

or (VIII and IX) or (VIII and X) or (VIII and IX and X),

-   where-   each of Ar⁴ to Ar⁹, independently of the others, is arylene which    may have from 6 to 18 carbon atoms, for example phenylene,    naphthylene or biphenylene. The arylene groups may be unsubstituted    or have substituents. These substituents include C₁-C₁₀-alkyl, such    as methyl, n-propyl, n-butyl or tert-butyl, and also C₁-C₄-alkoxy,    such as methoxy, ethoxy or butoxy. The substituents may also be    phenyl or halogen, in particular chlorine.-   u may be 0 or 1, and-   G is SO₂ or a 1,4-benzoquinone radical.

Examples of polyesters of this type are those which derive from one ormore of the following monomeric units: p-hydroxybenzoic acid,m-hydroxybenzoic acid, terephthalic acid, isophthalic acid,hydroquinone, phenylhydroquinone, alkyl-substituted hydroquinones, inparticular 2-methylhydroquinone, 2-ethylhydroquinone,2-n-propylhydroquinone, 2-isopropylhydroquinone or2-tert-butylhydroquinone, and halo-substituted hydroquinones, inparticular 2-chlorohydroquinone.

Other examples of suitable monomers are 4,4′-dihydroxydiphenyl ether,1,3-dihydroxybenzene, 4,4′-biphenol, 2,6,2′,6′-tetramethylbiphenol,2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,2,6-naphthalenedicarboxylic acid, 6-hydroxy-2-naphthalenecarboxylicacid, 4,4′-bis(p-hydroxyphenoxy)diphenyl sulfone,2,6-dihydroxyanthraquinone, 4,4′-diphenyl ether dicarboxylic acid and4,4′-dihydroxybenzophenone.

Other suitable polyesters derive from the abovementioned dicarboxylicacids and from aliphatic or cycloaliphatic polyols, preferably fromdiols. Possible diols are compounds of formula (XI)HO—R¹³OH  (XI)where R¹³ is C₂-C₁₈-alkylene, preferably C₂-C₁₀-alkylene, in substitutedor unsubstituted form, e.g. ethylene, propylene, butylene, pentylene, orhexylene. It is particularly preferable for there to be a bond betweenone of the two hydroxyl groups and the first and, respectively, the lastcarbon atom in the longest carbon chain. R¹³ may also be acycloaliphatic, unsubstituted or substituted, radical having from 3 to12 carbon atoms, preferably from 5 to 8 carbon atoms, for examplecyclopropylene, cyclopentylene or cyclohexylene. Preferred diols areethylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,6-hexanediol, 1,10-decanediol and 1,4-cyclohexanedimethanol.

Particularly preferred novel molding compositions comprise, as componentF, liquid-crystalline copolyesters with repeat units of the structure

These copolyesters generally contain from 10 to 90 mol % of the units(XII) and from 10 to 90 mol % of the units (XIII).

Other possible liquid-crystalline polymers F are polyesteramides whichhave repeat units of the structure

either by themselves or combined with other units, such as IX, X or XI.The radical L may be hydrogen, C₁-C₁₀-alkyl, e.g. methyl, ethyl,n-propyl, isopropyl or n-butyl, preferably methyl, C₁-C₁₀-alkoxy, suchas methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy, preferablymethoxy, or halogen, preferably chlorine.

The molar masses M_(w) (weight-average) of the liquid-crystallinepolymers used according to the invention as component F are generallyfrom 1500 to 150,000 g/mol, preferably from 2500 to 50,000 g/mol.

Liquid-crystalline polymers of this type are known per se or may beprepared by known methods.

Suitable preparation methods are mentioned in U.S. Pat. No. 4,161,470,for example. Other preparation methods may be found in EP-A 139 303, 226839, 226 978, 225 539, 226 847 and 257 558, for example, and referencemay be made to these at this point for further details.

The novel molding compositions may be prepared by known processes, forexample by extrusion.

The molding compositions may be prepared, for example, by mixing thestarting components in customary mixing equipment, such as screwextruders, preferably twin-screw extruders, Brabender mixers or Banburymixers, or else in kneaders, followed by extrusion. After extrusion theextrudate is usually cooled and comminuted.

The sequence of mixing the components may be varied, and two or, ifdesired, three components may therefore be premixed, or else all of thecomponents may be mixed together.

To obtain a very homogeneous molding composition, intensive and thoroughmixing is advantageous. The average mixing times required for this aregenerally from 0.2 to 30 minutes at from 280 to 370° C., preferably from290 to 360° C.

Together with good mechanical properties, such as high heat resistance,notched impact strength or stiffness, the novel molding compositionsparticularly feature improved stability during processing, in particularmelt stability, and improved flow properties.

The novel molding compositions are suitable for producing moldings,films or fibers. Examples of application for these are household items,electrical or electronic components and devices in medical technology.They are particularly suitable for producing moldings for the motorvehicle sector, in particular in the automotive sector. Examples ofthese are inlet manifolds, water tanks, housings, ventilation pipes,fastening components, sleeves and cooling fan wheels.

EXAMPLES

Test Methods:

The viscosity number (VN [ml/g]) of the polyarylene ether sulfones wasdetermined in a 1% strength by weight solution using N-methylpyrrolidoneat 25° C.

The viscosity number (VN [ml/g]) of the polyamides was determined to DIN53 727 on a 0.5% strength by weight solution in 96% strength by weightsulfuric acid at 25° C.

The proportion of acid groups in the polyarylene ether sulfones a2 wasdetermined by ¹H-NMR spectroscopy, as described by I. W. Parsons et.al., Polymer 34, 2836 (1993).

The glass transition temperature T_(g) and the melting peak weredetermined using DSC measurements on specimens in the second heatingcycle with a heating rate of 20 K/min.

The heat resistance of the specimens was determined by using the Vicatsoftening point (Vicat B [° C.]). This was determined on standard smallspecimens to DIN 53 460 with a force of 49.05 N and a temperature riseof 50 K/h.

Notched impact strength (a_(k) [kJ/m²]) was determined on ISO specimensto ISO 179 1eA.

Stiffness (modulus of elasticity) was determined to DIN 53 457.

Flowability (MVR [ml/10′]) was determined to DIN 53 735 at 300° C. witha load of 10 kg.

As a measure of melt stability, the change in the viscosity was followedover a period of 30 minutes in a capillary rheometer at 350° C. Thepercentage fall in the viscosity after 30 minutes is given, based on thestarting level (Δη[%]).

Preparation of the Molding Compositions

Component A

a1) Polyarylene Ether Sulfone Inert to Polyamides

A polyarylene ether sulfone having repeat units of the formula I₁,Ultrason® E 2010, a commercially available product from BASF AG, wasused as A1. A characteristic feature of this product is a viscositynumber of 54 ml/g, measured on a 1% strength NMP solution at 25° C.

a2) Functionalized Polyarylene Ether Sulfone Capable of Reacting withPolyamides

Component A2 Was Prepared as Follows:

5.742 kg of dichlorodiphenyl sulfone, 5.076 kg of dihydroxydiphenylsulfone and 305.8 g of 4,4′-dihydroxyvaleric acid were dissolved in 29kg of N-methylpyrrolidone under nitrogen and mixed with 2.820 kg ofanhydrous potassium carbonate. The reaction mixture was first heated for1 h to 180° C. at a pressure of 300 mbar while the water of reaction andN-methylpyrrolidone were continuously removed by distillation, and wasthen further reacted for 6 h at 190° C.

After addition of 40 kg of N-methylpyrrolidone, the inorganicconstituents were filtered off. Basic groups were neutralized by adding300 ml of glacial acetic acid, and the polymer was then isolated byprecipitation in water. After 3 extractions with water the product wasdried at 140° C. in vacuo, giving a white powder.

The proportion of units with acid groups was determined by ¹H-NMR at 3.0mol %, and the viscosity number of the product was 40.2 ml/g.

Component A3 Was Prepared as Follows:

4.593 kg of dichlorodiphenyl sulfone and 4.002 kg of dihydroxydiphenylsulfone were dissolved in 29 kg of N-methylpyrrolidone under nitrogenand mixed with 2.923 kg of anhydrous potassium carbonate.

The reaction mixture was first heated for 1 h to 180° C. at a pressureof 300 mbar while the water of reaction and N-methylpyrrolidone werecontinuously removed by distillation, and then further reacted for 6 hat 190° C.

After this time, 235 g of 4-fluorophthalic anhydride were added to themixture, and the reaction was continued for 0.2 h at 190° C.

After adding 40 kg of N-methylpyrrolidone, the inorganic constituentswere filtered off, and the polymer was then isolated by precipitation inwater. After 3 extractions with water, the product was dried at 160° C.in vacuo, giving a white material.

The content of phthalic anhydride end groups was 0.83% by weight, andthe viscosity number of the polyarylene ether was 49.7 ml/g.

Component B

A partly aromatic copolyamide, condensed from 55 parts by weight ofterephthalic acid, 35 parts by weight of ε-caprolactam and 38.5 parts ofhexamethylenediamine, was used as polyamide B1. Characterizing featuresof this material are a viscosity number of 210 ml/g, a glass transitiontemperature of 110° C. and a melting point of 289° C.

A nylon-6 obtained from ε-caprolactam and having a viscosity number of250 ml/g (Ultramid®B4, commercially available product from BASF AG) wasused as polyamide B2.

A nylon-6 obtained from ε-caprolactam and having a viscosity number of140 ml/g was used as polyamide B3.

Component C

Chopped glass fibers with polyurethane size, fiber diameter 10 μm, wereused as filler C1.

Component E:

Copper iodide, CuI, was used as stabilizer E1.

Component F:

A liquid-crystalline copolyester with repeat units of formulae XII undXIII was used as thermotropic polymer F1. Characterizing features ofthis polymer are a modulus of elasticity of 10.4 kN/mm² and atemperature T_(k) of about 280° C. for the transition determined by DSC.An example of a polymer of this type is the commercially availableproduct Vectra® A 950 from Ticona.

The components were mixed in a twin-screw extruder at a melt temperatureof from 300 to 350° C. The melt was passed through a water bath andpelletized.

The molding compositions were processed at 340° C. In each case the moldtemperature was 100° C.

Table 1 lists the makeups of the molding compositions and the results ofthe tests.

TABLE 1 Molding compo- sition 1c 1 2 3 2c 4 5 6 3c 4c Make up: A1 49 4847 41 49 48 47 41 49 48 A2 — — — 7 — — — — A3 — — — — — — — 7 — — B120.99 20.99 20.99 20.99 — — — — — — B2 — — — — 20.99 20.99 20.99 20.99 —— B3 — — — — — — — — 20.99 20.99 C1 30 30 30 30 30 30 30 30 30 30 E10.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 F1 — 1 2 1 — 1 2 1 — 1Proper- ties: Vicat B 206 206 207 206 204 203 203 203 204 204 [° C.]a_(k) 7.7 8.3 8.7 9.1 8.9 9.4 9.9 10.5 7.6 7.9 [kJ/m^(2]) Modulus 11.711.7 11.8 11.8 12.1 12.1 12.2 12.1 11.4 11.5 of elasti- city [kN/mm²]MVR 21 54 90 55 26 64 100 57 76 93 [ml/10′] Δη [%] 76 61 45 57 80 65 5060 84 86

The novel thermoplastic molding compositions have markedly improved flowproperties and melt stability together with very good mechanicalproperties.

1. A molding composition comprising A) from 1 to 98.8% by weight of atleast one polyarylene ether sulfone, B) from 1 to 98.8% by weight of atleast one thermoplastic polyamide, C) from 0.1 to 60% by weight of atleast one filler, D) from 0 to 40% by weight of at least oneimpact-modifying rubber, E) from 0 to 40% by weight of one or moredifferent additives, and F) from 0.1 to 30% by weight of at least onethermotropic polymer, where the total of the percentages by weight ofcomponents A to F is 100%, wherein component B has a viscosity number offrom 180 to 350 ml/g (measured in 0.5% strength by weight solution in96% strength by weight sulfuric acid to DIN 53 727).
 2. A moldingcomposition as claimed in claim 1, in which the polyarylene ethersulfone A contains from 0 to 100 mol % of repeat units

and from 0 to 100 mol % of repeat units


3. A molding composition as claimed in claim 1, where A is a mixturemade from at least one polyarylene ether sulfone a1 having groups whichare inert to the polyamides B and from at least one polyarylene ethersulfone a2 which contains groups which can react with the polyamides B.4. A molding composition as claimed in claim 3, in the polyarylene ethersulfones a2, the groups which can react with the groups in thepolyamides B are anhydride, carboxyl, epoxy or amino groups or a mixtureof these.
 5. A molding composition as claimed in claim 1, wherecomponent B is a partly aromatic polyamide.
 6. A molding composition asclaimed in claim 1, where component B is an aliphatic polyamide.
 7. Amolding composition as claimed in claim 1, which comprises from 0.01 to0.5% by weight, based on the total weight of A to F, of at least onecomponent E which is composed of copper(I) chloride, copper(I) bromide,copper(I) iodide or a mixture of these compounds.
 8. A moldingcomposition as claimed in claim 1, in which component F is athermotropic polyester, a thermotropic polyesteramide or a thermotropicpolyamide.
 9. A molding composition as claimed in claim 1, in whichcomponent F is a thermotropic copolyester containing repeat units of thestructures


10. A molding, a film or a fiber obtainable from the moldingcompositions as claimed in claim 1.